HU216092B - Bactericidal and fungicidal compositions containing complex compound of copper, and process for using thereof - Google Patents

Abstract

There is disclosed an improved copper complex bactericide/fungicide and a method of making and using the same. The improved bactericide/fungicide is prepared by forming an aqueous solution of a partially neutralized, water-soluble polycarboxylic acid having a molecular weight of between approximately 1,000 and 300,000 and a pH of between approximately 3 and 9. To this aqueous solution is added a copper-containing compound which when combined with said aqueous solution releases copper (II) ions which will form a water-soluble complex with said partially neutralized polycarboxylic acid. The water-soluble copper complex is applied to plants to prevent or inhibit bacterial and fungal disease growth thereon. <IMAGE>

Description

BACKGROUND OF THE INVENTION The present invention relates to copper complex bactericidal and fungicidal compositions and to methods of killing bacterial and fungal pests. The formulations contain copper complex and partially neutralized polycarboxylic acid.

Bactericidal and funcigid preparations are known in the art for the protection of agricultural plants against pathogenic bacteria and fungi. The use of these products is necessary because these organisms cause very large losses. From an economic point of view, the cost of plant protection using bactericidal and fungicidal formulations should be offset by increased yield and quality.

Agricultural bactericidal and fungicidal compositions may take a variety of forms including wettable powders, emulsifiable concentrates, water-based formulations and dry pourable formulations, also referred to as water-dispersible granules. Dry pourable formulations are generally powder-free, free-flowing granular products. These formulations have recently gained great popularity among users because of their improved shelf life, essentially dust-free, easy pourability and high active ingredient content, and their convenient packaging, which make them more favorable than other formulations.

Copper-containing bactericidal and fungicidal compositions are widely used in agriculture. Several dry liquid copper containing compositions are known, such as Kocide DF (Griffin Corporation of Valdosta, Georgia), Blueshield DF and Nu-Cop WDG (Micro Flo Company of Lakeland, Florida), and Sandoz COC and Sandoz Cu ₂ O DF (Sandoz Ltd, Switzerland).

Copper hydroxide alone is not stable. However, it is known that copper hydroxide can be stabilized by a phosphate process. For example, U.S. Patent Re 24,324 discloses a process for making stable copper hydroxide. U.S. Patent 3,428,731 relates to phosphate-stabilized copper hydroxide dispersions. The preparation of an aqueous dispersion of finely divided phosphate-stabilized copper hydroxide is described herein, wherein the pH of the dispersion and the calcium hardness of the aqueous carrier are carefully controlled. In the patent, about 1-3% by weight of the dispersion is to be added to the aqueous carrier prior to the addition of phosphate-treated copper hydroxide. Dispersing agents include, for example, sodium lignosulfonate, sodium salt of polymeric carboxylic acids, sulfonated naphthalenes, technical grade protein colloids, tallow dimethylbenzylammonium chloride, sodium salt of monosodium acid, polymerized alkyl aryl phenyl polyethoxyethanol is used.

However, prior art copper-containing bactericidal and fungicidal compositions require relatively large amounts of copper to be used effectively. However, this high copper content is disadvantageous in terms of cost, exacerbating soil residues problems and increasing the tendency to phytotoxicity. Furthermore, the preparation of such known compositions is not always economical.

Complexes of copper (II) ions with partially neutralized polycarboxylic acids and partially neutralized polymethacrylic acids in aqueous media are known [F. Wall and S. Gill, Interaction of Cupric Ions with Polyacrylic Acid, J. Phys. Chem., 58, 1128 (1954); Kotliar and H. Morawetz, Chelation of Copper (II) with Polyacrylic and Polymethacrylic Acid, J. Am. Chem. Soc., 77, 3692 (1955). However, it has not yet been known that copper complexes with partially neutralized polycarboxylic acids have bactericidal or fungicidal activity. In particular, it is not known that these complexes have agronomically useful bactericidal or fungicidal activity and are non-phytotoxic. Furthermore, it was not known that these complexes are effective against copper-tolerant bactericides or fungicides.

Therefore, there is a need for copper-containing bactericidal / fungicidal compositions which have biological activity against bacteria that are particularly susceptible to copper and are non-phytotoxic.

The formulations of the present invention meet the above need and have enhanced bactericidal / fungicidal activity. The bactericidal / fungicidal compositions of the present invention are prepared by dissolving the partially neutralized, water-soluble polycarboxylic acid having a molecular weight of 1000-300,000 in water, adjusting the pH of the water to 3-9, and adding the copper-containing compound to the aqueous solution releases copper (II) ions which form a water-soluble complex with the partially neutralized polycarboxylic acid.

The bactericidal / fungicidal compositions of the present invention are used to treat bacterial and fungal infections of plants by applying to the plant an effective amount of the compositions of the present invention comprising copper complex and partially neutralized water soluble polycarboxylic acid having a molecular weight of 1000 to 300000 a pH of 3-9.

Accordingly, the present invention relates to improved bactericidal / fungicidal compositions and their use.

It is another object of the present invention to provide bactericidal / fungicidal compositions which are non-phytotoxic to the plants to which they are applied.

It is another object of the present invention to provide bactericidal / fungicidal compositions which can be prepared using various sources of copper.

It is a further object of the present invention to provide bactericidal / fungicidal compositions suitable for killing copper resistant bacteria.

It is a further object of the present invention to provide bactericidal / fungicidal compositions which may also be applied to plants or crops which are known to be contaminated with known copper-containing bactericidal / fungicidal compositions.

EN 216 092 Β when applied in the optimum amount necessary for the control of pests.

It is another object of the present invention to provide bactericidal / fungicidal compositions which are substantially water-soluble so that they can be relatively easily removed from the crops or plants to which they have been applied and thus applied to the crop later in the growth and / or post-harvest cycle.

It is another object of the present invention to provide bactericidal / fungicidal compositions which do not discolor the plants or crops to which they have been applied.

It is another object of the present invention to provide bactericidal / fungicidal compositions which are also suitable for foliar application in pest control.

It is another object of the present invention to provide bactericidal / fungicidal compositions having the same protective activity as copper hydroxide-based bactericides / fungicides, even at lower copper contents.

It is another object of the present invention to provide bactericidal / fungicidal compositions which can be used to pre-treat seeds prior to planting.

It is another object of the present invention to provide bactericidal / fungicidal compositions suitable for inhibiting the growth of bacteria and / or fungi on substrates of various materials.

Figure 1 shows the copper concentration versus pH of neutralized polycarboxylic acid at a concentration of 1% by weight for three different sources of copper.

Figure 2 shows the copper concentration versus pH of neutralized polycarboxylic acid at a concentration of 1% by weight for three different polycarboxylic acids.

Figure 3 shows the copper concentration versus concentration of neutralized polycarboxylic acid for three different polycarboxylic acids.

Figure 4 shows the copper concentration versus neutralized polycarboxylic acid solution for three different polycarboxylic acids.

Figure 5 shows the copper concentration versus pH of neutralized polycarboxylic acid for three different neutralizing agents.

Figure 6 shows the colon diameter (mm) for Altemaria solani as a function of copper concentration (ppm) for three different sources of copper.

FIELD OF THE INVENTION The present invention relates to an improved bactericidal / fungicidal composition for use in agriculture comprising an active ingredient of a copper compound and an aqueous solution of a partially neutralized polycarboxylic acid having a pH of from 3 to 9, ammonia free and non phytotoxic to the plant. The present invention also relates to the use of these copper-containing bactericidal / fungicidal compositions in plants, harvested crops, seeds and various substrates for the control of bacterial fungal pests.

The novel compositions of the present invention exhibit enhanced biological activity relative to known copper-containing products, and this effect is achieved with significantly lower copper contents. Reduced copper content reduces the amount of copper accumulated in the soil. The bactericidal / fungicidal compositions of the present invention are non-phytotoxic to the plants to which they are applied and are particularly advantageous over other water-soluble copper-containing compositions.

The bactericidal / fungicidal compositions of the invention are prepared according to the following steps. An aqueous solution of the polycarboxylic acid is prepared by mixing the water-soluble polycarboxylic acid and water. The polycarboxylic acids used in the compositions of the invention may be homopolymers or copolymers of carboxylic acids. The aqueous solution of polycarboxylic acid is then partially neutralized with a basic material. To the resulting partially neutralized polycarboxylic acid solution is then added a copper-containing compound which liberates copper (II) ions in the solution, which react with the partially neutralized polycarboxylic acid to form a complex. The resulting copper complex is completely water soluble.

The copper and polycarboxylic acid content of the compositions of the invention is by weight unless otherwise indicated. The bactericidal / fungicidal compositions of the invention may also be prepared in the form of a dry composition by drying the aqueous solution after complexation. It will be appreciated that the percentage of copper and polycarboxylic acid will change after removing the water from the aqueous solution of the copper complex. However, this change can be readily calculated by one of ordinary skill in the art based on the amount (weight%) of the aqueous solution components.

Polycarboxylic acids useful in the compositions of the present invention are water soluble polycarboxylic acids having a molecular weight of 1000 to 300000, preferably 2000 to 50,000. The exact structure of the polycarboxylic acids is not critical to the invention. By way of example, the following polycarboxylic acids are mentioned: copolymers of polyacrylic acid, polymethacrylic acid, acrylic acid and acrylamide, copolymers of acrylic acid and methacrylamide, copolymers of acrylic acid and acrylate esters, copolymers of acrylic acid and methacrylic acid, acrylic acid and methacrylic acid, copolymers of methyl cellulose, maleic acid and butadiene, polymers of maleic acid and maleic anhydride, copolymers of maleic acid and acrylic acid, copolymers of methyl vinyl ether and maleic anhydride.

Non-water-soluble polycarboxylic acids can also be made suitable for use in the compositions of the present invention by converting water-insoluble polycarboxylic acid into a water-soluble salt of polycarboxylic acid. These methods are known in the art. Generally, such salts are prepared by reacting the polycarboxylic acid with a basic material. As the basic material, for example, sodium hydroxide, potassium hydroxide, NaHCO ₃ , Na ₂ CO ₃ , NH ₄ OH, R ₄ N®OH ^S , where R is CH ₃ or C ₂ H ₅ , primary amines , so for example

21 methyl, ethyl, η-propyl, isopropyl, tert-butylamines, secondary amines such as dimethyl, diethyl, di (npropyl) and diisopropylamines, and tertiary amines such as for example trimethyl, triethyl, tri (n-propyl) amines.

The concentration of the polycarboxylic acid in the aqueous solution is substantially non-existent. The polycarboxylic acid is added to water in an amount sufficient to react with the copper-containing compound to form a complex. However, as the concentration of polycarboxylic acid increases, the viscosity of the solution also increases. This is especially true for relatively high molecular weight polycarboxylic acids. It is generally undesirable for the aqueous solution to have a high viscosity in order to be effectively mixed with the copper-containing compound. Generally, the amount of polycarboxylic acid in the compositions of the invention is from 0.2 to 80% by weight, preferably from 0.75 to 20% by weight.

When the polycarboxylic acid is dissolved in water, the pH of the solution is acidic. It is critical to the invention to partially neutralize the polycarboxylic acid using a basic material such that the resulting solution has a pH of 3 to 9, preferably 3.5 to 5. In general, it has been observed that the amount of copper capable of complexing depends, at least in part, on the pH of the aqueous solution of the partially neutralized polycarboxylic acid. The amount of copper capable of complexing is maximum in the above-mentioned pH ranges. At pHs outside the pH range of 3-9, the amount of copper that can be complexed cannot be utilized in practice.

The nature of the materials used to neutralize the polycarboxylic acid is not critical to the invention. Suitable neutralizers include, for example: sodium hydroxide, potassium hydroxide, NaHCO _3, Na ₂ CO _3, NH ₄ OH, Κ, Ν®ΟΗ ^Θ, wherein R represents CH ₃ - or C ₂ H ₅ group , primary amines such as methyl, ethyl, η-propyl, isopropyl, tert-butylamine, secondary amines such as dimethyl, diethyl, di (n-propyl) and diisopropyl and tertiary amines such as trimethyl, triethyl, or tri (n-propyl) amines.

The resulting partially neutralized polycarboxylic acid is a combination of a polycarboxylic acid copolymer and a polycarboxylic acid salt such as sodium polyacrylate. Preferred partially neutralized polycarboxylic acids are commercially available. Examples include Goodrite K-752 (BF Goddrich Co., Cleveland, Ohio). Goodrite K-752 is a mixture of a polyacrylic acid and some of its sodium salt in water of the formula (C ₃ H ₄ O ₂ ) χ (C ₃ H ₃ NaO ₂ ) _y . Another suitable product is DP6-2696 and DISPEX N40, both of which are polymeric carboxylic acid salts in aqueous solution, both of Allied Colloids, Inc. of Suffolk, Virginia.

The copper-containing compounds useful in the compositions of the present invention are those which, in aqueous solution containing partially neutralized polycarboxylic acid, convert to copper ions, which then complex with the partially neutralized polycarboxylic acid present. Examples of such copper-containing compounds include Cu (OH) ₂ , CuSO ₄ , Cu (C 10 ₄ ) 2, Cu ₂ O, Cu (NO ₃ ) ₂ , CuCl ₂ , copper oxychloride, basic copper carbonate, and tribasic copper sulfate. Copper oxychloride has the chemical formula 3Cu (OH) ₂ .CuCl ₂ , basic copper carbonate Cu (OH) ₂ .CuCO ₃ and tribasic copper sulfate has the formula 3Cu (OH) ₂ .CuSO ₄ .

The copper-containing compounds may be soluble in water, such as CuSO _4, Cu (C10 _{4) 2,} Cu (NO _{3) 2} and CuCl _2, or substantially water insoluble, such as Cu (OH) _2, Cu ₂ O, tribasic copper sulfate, basic copper carbonate or copper oxychloride. Water-insoluble copper-containing compounds have not been known to form complexes.

Copper hydroxide compounds useful in the compositions of the present invention include technical grade copper hydroxide compounds (phosphate stabilized, such as those described in U.S. Patent Re 24324 and U.S. Patent No. 3428731) and copper. hydrate, which is a purer form of copper hydroxide. Other stabilized copper hydroxides may also be used.

Copper-containing compounds useful in the compositions of the present invention are commercially available. Such is, for example, KOCIDE copper hydroxide, a phosphate stabilized copper hydroxide for use in agricultural fungicides, containing 88% by weight of copper hydroxide and 12% by weight of inert material, which is a product of Griffin Corporation of Valdosta, Georgia. Methods for the preparation of phosphate-stabilized copper hydroxides are disclosed in the aforementioned U.S. Patents.

The amount of copper-containing compound added to the partially neutralized polycarboxylic acid solution is that useful in the final bactericidal / lungicidal composition. In general, when preparing the bactericidal / fungicidal composition of the invention, it is desirable to complex as much copper as possible with the partially neutralized polycarboxylic acid. Factors affecting copper complexation include the pH of the aqueous solution of the partially neutralized polycarboxylic acid, the molecular weight of the polycarboxylic acid, and the concentration of the partially neutralized polycarboxylic acid.

In general, it has been observed that if the water-insoluble copper-containing compound is in excess of that which can be complexed with the polycarboxylic acid, the excess copper-containing compound is insoluble in the aqueous solution. This can be considered as an unfavorable situation. If a solid, water-insoluble copper-containing compound is undesirable in the composition of the invention, it may be removed from the liquid portion by known means, such as filtration. Excess water-soluble copper-containing compounds are present in solution in the form of uncomplexed copper ions. Such uncomplexed copper ions can make the solution phytoxotic. Therefore, if the copper complex of the partially neutralized polycarboxylic acid is derived from a water-soluble, copper-containing compound, the amount of such copper-containing compound should be chosen to react sufficiently with the polycarboxylic acid.

EN 216 092 Β well-uncomplexed copper ion, which then renders the solution phytotoxic.

The amount of copper from the copper-containing compound that can be used in the compositions of the invention is 0.1 to 5% by weight (metal copper equivalent), preferably 0.1 to 3.2% by weight (metal copper equivalent).

The aqueous copper complex solution may be used to treat plants in liquid form as obtained by the above process, or may optionally be dried to a solid which may then be dispersed repeatedly in water to form an aqueous solution for spray application. The drying of the aqueous copper complex solution can be carried out using known drying equipment, such as an oven or spray dryer or freeze-drying. In the case of spray drying, the spray drying device is either equipped with a single fluid nozzle or a hydraulic nozzle or rotary disk atomizer may be used. Such spray dryers generally have an inlet temperature of 170 to 250 ° C and an outlet temperature of about 65 to 125 ° C. Spray drying equipment and methods are known in the art. Freeze drying equipment and these methods are also known. By using known methods, the bactericidal / fungicidal compositions of the present invention can be prepared in a variety of forms, such as in the form of flakes, powders, granules or solutions.

The bactericidal / fungicidal compositions of the invention can be applied directly to the leaves of the plants to control bacterial / fungal pests. The bactericidal / fungicidal compositions may be applied to the plants in the liquid form obtained as described above or, after drying, in a water-mixed form, using known agricultural sprayers and spraying methods. Bactericide / fungicide liquid compositions of the invention are preferably diluted with water is applied to foliage of plants by spraying (either in the air or soil by spraying) or by using kemigációt 0.1 to 6.0 kg / ha, in an amount from 3.8 to 10 ~ ³ fémrézekvivalens —3.1 m ^3/4 · 10 ³ m ² water volume.

The bactericidal / fungicidal compositions of the present invention are useful in the treatment of a variety of plants for bacterial and fungal diseases such as citrus fruits such as grapefruit, lemon, lime lemon, orange, tangelo and tangerine; outdoor plants such as alfalfa, oats, peanuts, potatoes, sugar beet, wheat and barley; small plants such as blackberries, cranberries, currants, gooseberries, raspberries and strawberries, woody plants such as almonds, apples, peaches, avocados, bananas, cocoa, cherries, coffee, peanuts, mangoes, peaches, olives, peaches , pears, pecans, plums, rockets and nuts; vegetables such as beans, broccoli, Brussels sprouts, cabbage, cantaloupe, carrots, kohlrabi, celery, American cabbage, cucumbers, egg fruits, various melons, onions, peas, pepper, pumpkin, pumpkin, tomato and watermelon; grapes such as grapes, hops and kiwi; and other miscellaneous plants such as ginseng, oak and sycamorph, and ornamental plants such as aralia, azalea, begonias, tubers (lilies, tulips, gladioli), carnation, chrysanthemum, avian, gooseberry, hawthorn, wild amber, philodendron, roses and yucca (Adams-Needle).

The bactericidal / fungicidal compositions of the present invention are useful in the treatment of a variety of bacterial and fungal diseases, such as pigmentation, scabies, pinkish-scaly, greasy mottling, brown rot, phytophthora, citrus goiter, xanthomodel, (alternaria), alternative drying, botrytis drying, powdery mildew, xantomonas leaf blotch, anthracnose, pseudomonas leaf blotch, septoria leaf blotch, entomosporium leaf blotch, volutella leaf blotch, phomopsis blemish, bacterial leaf blight, , flower drying, pseudomonas drying, root and root rot (Phytophthora cactorum), band leaf blotch (Cristulariella pyramidalis), walnut drying, bacterial drying (cyclic and common), brown blotch, black rot (xanthomonas), downy mildew, cercospora early drying (blotching), septoria late drying, square leaf blotch, phomopsis, purple blotching, bacterial blotching, gray leaf blotch, erythema leafworm, septum , Pseudomonas fluorescens, stem drying, lumpy moss, leptosphaerulina leaf blotch, helmitosporium leaf blotch, leaf blotch, reed rot, fruit rot, fruit flower rotting, bacterial blight Collectotrichum coffeanum), leaf rust (Hemileia vastatrix), iron blotch (Cercospora coffeicola), pink disease (Corticium salmonicolor), hazelnut drying and peacock blotch.

Certain strains of bacteria have become resistant to conventional copper-containing bactericides. However, the bactericidal / fungicidal compositions of the present invention are particularly suited to combating diseases caused by copper-resistant bacterial strains such as Xanthomonas campestris and Pseudomonas syringae.

Because the bactericidal / fungicidal compositions of the present invention are water-soluble, they can be used in a variety of plants or crops and are relatively easy to remove by washing or spraying with water. As a result, the bactericidal / fungicidal compositions of the invention may also be used in the late growth cycle of crops, which would not be possible with known bactericidal / fungicidal compositions. Further, the bactericidal / fungicidal compositions of the invention can also be used to treat crops after harvest, such as oranges, citrus fruits, cucumbers and apples, thereby forming a protective coating which can be easily removed by subsequent washing.

HU 216 092 Β

The bactericidal / fungicidal compositions of the present invention do not leave a discolored stain upon application to the plants and as is the case with known copper-containing bactericidal / fungicidal compositions. Thus, the bactericidal / fungicidal compositions of the invention can be used in seedlings and ornamental greenhouses.

The reduced phytotoxicity of the bactericidal / fungicidal compositions of the present invention allows them to be used on sensitive plants and crops, such as peaches, pears, apples or lettuce, which are otherwise damaged by known copper-containing bactericidal / fungicidal compositions when required for pest control. applied in optimal amounts.

The bactericidal / fungicidal compositions of the invention may also be used to treat seeds prior to planting. The bactericidal / fungicidal compositions of the present invention are treated in a known manner, for example, by spraying the compositions onto the core and then allowing it to dry to form a coating on the core. The seed so treated is then treated and planted in a known manner, so that it is treated in the same manner as the seed treated with a known copper-containing bactericidal / fungicidal composition. The bactericidal / fungicidal compositions of the present invention are particularly suitable for killing inocula in the seed and preventing infection of the germinating seedlings or seeds. Although the bactericidal / fungicidal compositions of the present invention are generally useful for seed treatment, they are particularly preferred for example rice, wheat, cotton, soybeans, beans, corn and hazelnuts.

The application rates of the bactericidal / fungicidal compositions of the present invention after application on the surface of the plants may be increased by the addition of certain agents to the concentrated compositions or spray solutions. Examples of such agents include, but are not limited to, polyvinylpyrrolidone (PVP), polyethyleneoxy-leached derivatives, polyvinyl alcohol), and polyacrylamide. These compounds are known in the art as thickeners. The thickeners are added to the composition in an amount that is necessary to provide rain resistance without adversely affecting the bactericidal / fungicidal properties of the copper-containing solution. The amount of thickeners is generally in the range of 0.1 to 10% by weight.

It has been observed that the amount of copper capable of complexing with partially neutralized polycarboxylic acid depends on the molecular weight of the polycarboxylic acid. Generally, the higher the molecular weight of the polycarboxylic acid, the more copper can be complexed with it. However, as noted above, increasing the molecular weight of the polycarboxylic acid increases the viscosity. Thus, the choice of polycarboxylic acid should also take into account the desired copper content and viscosity.

The bactericidal / fungicidal compositions of the present invention may also be used to treat substrates other than plants and crops. For example, the bactericidal / fungicidal compositions of the invention may also be used to treat various bacterial and fungal diseases on other non-living substrates such as textiles, metals, glass, wood and paper, foams, concrete, stones and other materials. In treating these, the bactericidal / fungicidal compositions of the present invention are applied to the surface in a manner known in the art, such as by spraying, painting, immersion or the like. If desired, the bactericidal / fungicidal composition may be applied by impregnation with suitable substrates. The bactericidal / fungicidal compositions of the present invention may also be used against various bacterial and fungal growths in hospital and medical environments, such as clothing, materials, rugs, ceramic and linoleum floors, and plastic surfaces. In such use, the copper complex of the present invention is used in an amount sufficient to prevent or prevent the growth of bacteria and / or fungi on the treated surface. The amount of copper complex applied will depend on the type of material being treated and the conditions under which the material is present. Generally, the application rate of the bactericidal / fungicidal compositions of the present invention is from 1 to 1000 mg copper (metal equivalent) / cm ² .

The following examples further illustrate the present invention without limiting it.

Example 1

959 g of water are mixed with 40 g of Goodrite 75-752 (63% aqueous polyacrylic acid solution, molecular weight 2100) and the resulting solution is neutralized to pH 7 with 50% sodium hydroxide. The solution is then stirred at room temperature to completely dissolve the partially neutralized Goodrite K-752 in water. To the solution was then added 1.42 g of Cu (OH) ₂ (56.4% of copper), and the mixture was stirred for 12-24 hours to completely dissolve the Cu (OH) ₂ . The resulting clear blue solution was analyzed for copper. The solution was found to contain 800 ppm copper.

Example 2

113.4 g of Goodrite 75-752 are dissolved in 433.8 g of water and 21.4 g of 50% NaOH are adjusted to pH 4.5. To the partially neutralized Goodrite K-752 solution was added 789 g of water and stirred until complete homogeneity. To the solution was then added 32.3 g of copper hydrate (62% metal copper), and the mixture was stirred for 12-24 hours until the copper hydrate was completely dissolved. The resulting clear blue solution contains 2% by weight copper (metal copper equivalent).

Example 3

An aqueous solution was prepared by mixing 940 g of deionized water and 60 g of Goodrite K-752 (63% aqueous polyacrylic acid solution, molecular weight 2100) and neutralized to pH 7 with 50% sodium hydroxide. The solution is then stirred at room temperature until the Goodrite K-752 is completely dissolved. Partially so

To the neutralized aqueous solution was added 10 g of CuOH ₂ , and the resulting dispersion was stirred for 24-48 hours until the reaction between the copper hydroxide and the partially neutralized polyacrylic acid was complete. Since copper hydroxide is essentially insoluble in water, excess, undissolved copper hydroxide remains in solid form in the dispersion. The dispersion is then filtered to separate the liquid phase and solid copper hydroxide using a 0.2 μιη filter. The content of copper in the filtrate was determined to be 1270 ppm Cu (metal equivalent).

Example 4

An aqueous solution was prepared by mixing 989 g of water and 10 g of Goodrite K-752 (63% aqueous polyacrylic acid solution, molecular weight 2100) and neutralizing the solution to pH 7 with 50% sodium hydroxide. The solution is then stirred to dissolve Goodrite K-752 in water. The thus partially neutralized aqueous solution was added 1 g of CuSO ₄ on added and the mixture was stirred at the copper sulfate for about 30 minutes to ensure complete dissolution. The copper content is then determined by analysis, which is 800 ppm Cu (metal equivalent). The solution is tested for biological activity and is found to be substantially non-phytotoxic, similarly to an aqueous dispersion of known aqueous copper hydroxides containing the same amount of copper. However, an equal amount of free ionic copper causes severe plant damage and death.

Example 5

An aqueous solution is prepared by mixing 1000 g of water with 20 g of Goodrite K-752 (polyacrylic acid, molecular weight about 2100). The solution is then stirred at ambient temperature to ensure the Goodrite K-752 is soluble in water. Sodium hydroxide is then added to the solution so that Goodrite 75-752 is partially neutralized to a pH of about 7. To this partially neutralized aqueous solution is added 2 g of CuCl ₂ and the mixture is stirred for about 30 minutes to dissolve the copper chloride. The copper content of the solution is then determined to be 1000 ppm Cu (metal equivalent).

Example 6

An aqueous solution was prepared by mixing 960 g of water and 40 g of Goodrite K-752 (63% aqueous polyacrylic acid solution, molecular weight 2100) and neutralized to pH 7 with 50% sodium hydroxide. The solution is then stirred at room temperature until complete dissolution, then 10 g of copper oxide chloride is added to the partially neutralized aqueous solution, and the aqueous dispersion is stirred for about 24 to 48 hours to ensure complete complexation. Since the copper oxychloride is essentially insoluble in water, the excess copper oxide chloride, which remains in the solid form in the dispersion, is filtered off using a 0.2 µm filter. The filtrate was then analyzed for its copper content of 325 ppm Cu (metal equivalent).

Example 7

Six samples, each containing 800 ppm of copper (four times the estimated LD ₉₀ value of 200 ppm for Colletotrichum lagenarium on cucumbers) were prepared using copper copper sulfate. Copper is complexed with partially neutralized (pH 7, sodium hydroxide) polycarboxylic acid (Goodrite K-752) in aqueous solution. The polymer content of the various samples in% is 4%, 2%, 1%, 0.75%, 0.5% and 0.25%. Samples with 4%, 2% and 1% polymer content are clear blue solutions, although the color becomes greener as the polymer content decreases. Below 0.75% of the polymer, a blue-green precipitate is formed and a colorless upper layer is formed. An excess of copper is believed to cause the polymer to become insoluble, presumably through crosslinking. Samples with 4% to 0.75% polymer content are essentially non-phytotoxic against cucumbers under greenhouse conditions, with samples containing 1% and 0.75% polymer showing the lowest phytotoxicity. These samples have bactericidal and fungicidal activity against Colletotrichum lagenarium on cucumber plants. Cucumber plants were also treated with the same amount of free ionic water from copper sulfate, and in these cases severe damage and necrosis were observed. In plants treated with copper sulphate, efficacy could not be assessed due to severe damage.

Example 8

Examples 1 and 4 provide polycarboxylic acid copper complexes using CuSO ₄ and Cu (OH) ₂ as the copper source. For each source of copper, the copper content of the samples is 800, 400, 200 and 100 ppm copper, respectively. Cumulative phytotoxicity assays were performed on tomato and pepper plants. Samples were applied to plants four times at 1 week intervals. No phytotoxicity was observed in either case.

Example 9

Copper polycarboxylic acid complexes were prepared as described in Example 1, except that the molecular weight of the polyacrylic acid and the pH of the partially neutralized polyacrylic acid solution were changed. Polyacrylic acids of various molecular weights were obtained from BF Goodrich: Goodrite K-752 (molecular weight 2100), Goodrite K-732 (molecular weight 5100), Goodrite K-XP82 (molecular weight 2800), and Goodrite K-XP83 (molecular weight 5800) ). An aqueous solution of the polymers was prepared, each solution containing 1.6% polymer. The samples were neutralized with sodium hydroxide to the pH in the following table. Copper complexes were prepared from neutralized samples by addition of excess Cu (OH) ₂ . Samples were filtered through a 0.22 µm filter and the copper content was determined. The results are summarized in Table 1 below.

HU 216 092 Β

Table 1

Polyacrylic acid (PAA) Napa pH PH of the filtered solution containing the complex Cu (ppm) Goodrite K-752 5.0 6.9 2940 Goodrite K-752 5.7 7.6 1320 Goodrite K-752 6.7 9.2 503 Goodrite K-752 7.0 9.5 500 Goodrite K-752 7.6 9.9 770 Goodrite K-732 5.0 7.0 3086 Goodrite K-732 5.5 8.0 2840 Goodrite K-732 6.0 8.6 1095 Goodrite K-732 6.6 9.5 444 Goodrite K-732 7.1 9.8 795 Goodrite K-732 7.6 10.0 200 Goodrite K-XP82 7.1 9.7 119 Goodrite K-XP83 7.1 9.7 217

As shown in Table 1, although the results are significantly scattered, the pH has a greater influence on the amount of copper that can be introduced into the complex than the molecular weight, which ranges from 2100 to 5800.

Further samples were prepared as described above using three different polymers and copper hydrate as the copper source. Goodrite K-752 (polyacrylic acid, molecular weight 2100), Colloid WJ61 (polyacrylic acid, molecular weight 60,000, manufactured by Rhone-Poulenc) and Colloid 204 (polyacrylic acid, molecular weight 10,000, manufactured by Rhone-Poulenc) were used as polymers. The results of the assays are shown in Figure 2, where the copper concentration, expressed in metal equivalent, is plotted against the pH of the neutralized polymer solution, where the concentration of polyacrylic acid is 1% by weight. As shown in Figure 2, the pH of the neutralized polymer is the determining factor for copper that can enter the complex, but the highest molecular weight polymer (Colloid WJ61) is able to complex significantly higher amounts of copper than the other polymers tested. -6 pH range.

Using the above copper complex solutions, the complex copper content of the solutions was measured at which the pH of the partially neutralized polycarboxylic acid solution was optimal and the amount of polymer ranged from 1 to 10% by weight. The test results are summarized in Figure 3, where copper concentration is plotted against polymer concentration for each of the three polymers.

Example 10

Following the procedure described in Example 3, polycarboxylic acid copper complexes were prepared with the difference that the pH of the partially neutralized polycarboxylic acid was different for the different samples. The complexes were prepared in 1% by weight polymeric solutions of polyacrylic acid (Goodrite K-752), which were partially neutralized with sodium hydroxide to a pH of 3-8.5. Copper from various sources of copper was then added in excess to the partially neutralized polymer solutions. One source of copper is technical grade copper hydroxide (phosphate stabilized material according to U.S. Patent Re 24,324 and U.S. Patent 3,428,731), another source of copper is copper hydrate (a purer form of copper hydroxide), and basic copper carbonate was used as the source. The liquid portion of the samples was separated from the solid copper-containing compound and the filtrate analyzed for copper. The results obtained are shown in Figure 1, where the concentration of copper (in metal equivalent) is plotted against the pH of the neutralized polymer solutions.

The figure shows that when technical grade copper hydroxide is used as a source of copper, the copper complexes at a maximum pH of about 4.5. In the case of a copper hydrate source, the maximum copper complexation occurs at the same pH but is able to complex about 35% more copper with the same amount of polyacrylic acid. The impurities present in the technical grade copper hydroxide, most likely the various salts, appear to affect the complexing ability of the polymer.

Example 11

Using copper from various sources, polyacrylic acid copper complexes are prepared by adding the copper-containing compound to a partially neutralized aqueous solution (pH 7, sodium hydroxide) of 4% Goodrite K-752. Samples were prepared as described in Examples 3 and 4, depending on whether the copper used was water-soluble or non-water-soluble. The copper sources used were: copper chloride, copper oxychloride, copper oxide and basic copper carbonate. In each case, copper complexes were formed with the partially neutralized polyacrylic acid.

Example 12

Copper polyacrylic acid complex is prepared by adding 1.5% by weight copper (metal equivalent) which is introduced as copper hydroxide into a 12% by weight aqueous solution of Goodrite K-752 solid, neutralized to pH 4.8 with sodium hydroxide. The resulting mixture is stirred for about 12 hours to give a clear blue solution which does not contain undissolved copper hydroxide. The solution was then freeze-dried using a Labconco lyophilizer at -50 ° C under vacuum. The product obtained is a blue honeycomb-like solid which is very soluble in water to form a blue-green solution. The dry product contains 8.57% copper and 5% water. The dry powder X-ray diffraction pattern showed no peak, indicating that the dry copper complex was not crystalline.

Example 13

Copper polyacrylic acid complexes are prepared with different molecular weight poly8 purchased from Polysciences

Using an acrylic acid, copper was added in excess in the form of copper hydroxide to prepare complexes to a partially neutralized aqueous solution of 1 wt% polyacrylic acid (pH = 5, sodium hydroxide). The liquid portion was separated from the solid copper hydroxide by filtration and the filtrate was determined for copper. The following Table 2 summarizes the maximum copper contents in the complexes.

Table 2

molecular Weight Cu concentration (ppm) 2000 2330 5000 2730 50000 3500 90000 3530 150000 3200

Example 14

Copper complexes of polycarboxylic acids are prepared using three different polymers. The three polycarboxylic acids are: Alcosperse 475-2 (70/30 molar acrylic acid maleic acid copolymer, molecular weight 20,000, manufactured by Alco Chemical Corp.), Gantrez AN-119 (50/50 molar methyl vinyl ether and maleic anhydride copolymer, molecular weight). 20000, manufactured by GAF Corp.) and Goodrite K-752. The complexes are prepared by preparing a 1% by weight aqueous solution of polyacrylic acid (Goodrite K-752), neutralizing it with sodium hydroxide to a pH of 2.5-9, and adding excess copper hydroxide. The undissolved solid copper hydroxide was removed by filtration and the copper content of the filtrate was determined. The results obtained are shown in Figure 4, where the copper content of the complexed product is plotted against the pH of the neutralized polymer solution. The study shows that all three polymers complex with copper. These copper complexes are biologically active in Altemaria solani and Xanthomonas campestris pv. against vescatoria strains.

Example 75

Copper polyacrylic acid complexes are prepared as described in Examples 3 and 4, depending on whether or not the copper source used is water soluble. The liquid portion of the copper complexes is Xanthomonas campestris pv. efficacy against the Vescatoria strain. Copper complex samples of different concentrations were prepared using Casitone yeast extract (CYE) medium at concentrations of 1, 2, 4, 6, 8, 10, 20, 40, 60, 80 and 100 ppm, expressed as copper. These were compared with samples containing the same amount of copper sulfate, since it is known that copper in this form is on biologically active agar medium. Bacterial cultures in CYE medium were then agar-stained and incubated for 5 days at 27 ° C. The degree of death was determined on the basis of the presence or absence of bacterial strains. Each copper complex sample as well as copper sulfate samples kill bacteria at 6 ppm and above. This assay showed that the copper complex samples of the present invention were as active as the copper sulfate samples. The results obtained are summarized in Table 3 below.

Table 3

Poly acrylic acid copper source ld _{95 on} CYE agar polyacrylic acid copper hydroxide 6 polyacrylic acid copper sulfate 6 polyacrylic acid Cu (C10 ₄ ) ₂ 6 polyacrylic acid Cu ₂ O 6 polyacrylic acid Cu (NO ₃ ) ₂ 6 polyacrylic acid CuCl ₂ 6 polyacrylic acid Copper oxychloride 6 polyacrylic acid tribasic copper sulfate 6 polyacrylic acid basic copper carbonate 6 polyacrylic acid copper hydrate 6 polymethacrylic copper hydrate 6 copolymer of acrylic acid and acrylamide copper hydroxide 6 copolymer of acrylic acid and methacrylic acid copper hydroxide 6 copolymer of acrylic acid and acrylate ester copper hydroxide 6 copolymer of acrylic acid and methacrylic acid copper hydroxide 6 copolymer of acrylic acid and acrylamide copper hydroxide 6 copolymer of acrylic acid and methacrylate ester copper hydroxide 6 copolymer of acrylic acid and maleic anhydride copper hydroxide 6 a copolymer of carboxymethylcellulose maleic acid and butadiene copper hydroxide 6 maleic acid and maleic anhydride copolymer copper oxide 6 no copper sulfate 6

Example 16

The following Table 4 summarizes the polyacrylic acid copper complexes. The liquid portions of the copper complexes were then tested for efficacy against altemaria solani. Copper complexes were assayed in CYE medium in which the fungi to be examined were inoculated. The medium was used to prepare samples of varying concentrations with a copper content of 1, 10,

HU 216 092 Β

20, 40, 60, 80 and 100 ppm. For comparison, copper sulfate was used in similar amounts since it is known to be biologically active in agar medium. Active-growing Altemaria solani samples were taken from the outer perimeter of the colonies using a 7 mm stopper and placed in the middle of culture plates containing copper-containing media. The resulting samples were incubated at 28 ° C for 10 days and then the colonies were determined to determine if copper influenced fungal growth. The LD ₉₀ value for copper complex samples is 100 ppm copper and for copper sulfate this value is 80 ppm copper. These assays show that the copper complex samples of the present invention are essentially as active as the copper sulfate samples. The test results for samples obtained with different polycarboxylic acids and different copper sources are summarized in Table 4 and Figure 6.

Table 4

PAA concentration solid t% PAA Mole. crowd Partially neutralized pH of PAA copper source Example number Concentration of copper in the complex LD ₉₀ CYE agaron ppm Cu 2.50 2100 7.0 copper hydroxide 3 1270 ppm 100 1.67 * 2100 7.0 copper hydroxide 1 800 ppm 100 0.42 * 2100 7.0 copper sulfate 4 800 ppm 100 6.67 2100 5.3 copper hydrate 1 1.01% 100 6.67 2100 5.0 copper hydrate 1 1.01% 100 0.64 2100 4.8 copper hydroxide 1 1000 ppm 100 1.74 2100 4.8 copper hydroxide 1 2000 ppm 100 1.30 2100 4.8 copper hydroxide 1 2000 ppm 100 12.00 ** 2100 4.8 copper hydroxide 12 1.51% 100 1.20 2100 7.0 cupric chloride 5 1030 ppm 100 1.67 2100 7.0 Copper oxychloride 6 325 ppm 100 7.14 2100 4.5 copper hydrate 2 2.01% 100 20.00 2100 4.5 copper hydrate 1 3.5% 100 1.00 5000 5.2 copper hydroxide 3 2730 ppm 100 1.60 5800 7.1 copper hydroxide 3 220 ppm 100 5.00 10000 4.1 copper hydrate 3 1.2% 100 1.00 50000 5.0 copper hydroxide 3 3500 ppm 100 2.85 60000 4.1 copper hydrate 1 1.01% 100 1.00 90000 5.0 copper hydroxide 3 3530 ppm 100 1.00 150000 5.0 copper hydroxide 3 3200 ppm 100 1.00 240000 5.0 copper hydroxide 3 3150 ppm 100 no copper sulfate 3 80

* Examination of Complexes in Figures 1 and 6 ** Both the copper complex solution and the freeze-dried material contain 8.571% copper, as in Example 12.

Example 17

The following Table 5 summarizes the polyacrylic acid copper complex samples. The liquid portion of the copper complexes is derived from Xanthomonas campestris pv. against the strain vescatoria, which is known to be resistant to known copper-containing bactericidal / fungicidal compositions. Samples were prepared as described in Example 12 and loaded on agar for assay. Copper complexes were assayed on CYE agar inoculated with the desired bacterium, and the copper content of the samples was adjusted to the following values using the medium, expressed as metal copper:

50,100, 200 and 300 ppm. For comparison, copper sulfate is used in similar amounts since it is known to be in biologically active agar medium. Bacterial cultures obtained in CYE medium were agar-supplemented with 25 ppm copper and incubated at 5 ° C for 5 days. The death rate was defined as the presence or absence of bacterial colonies. Copper complex samples kill copper-resistant bacteria at a concentration of 300 ppm, whereas copper sulfate has a concentration of 300 ppm.

The results of the assays are summarized in Table 5 below.

HU 216 092 Β

Table 5

PAA concentration solid t% PAA Mole. crowd Partially neutralized pH of PAA copper source Example number Concentration of copper in the complex ld ₉₀ cye agaron ppm Cu 1.67 2100 7.0 copper hydroxide 1 800 ppm 300 0.42 2100 7.0 copper sulfate 4 800 ppm 300 6.67 2100 5.3 copper hydrate 1 1.01% 300 6.67 2100 5.0 copper hydrate 1 1.01% 300 12.00 * 2100 4.8 copper hydroxide 12 1.5% 300 0.80 2100 4.8 copper hydrate 1 2000 ppm 300 1.06 2100 4.8 copper hydrate 1 2000 ppm 300 1.60 2100 4.8 copper hydrate 1 2000 ppm 300 3.75 2100 4.5 copper hydrate 1 1.01% 300 6.25 2100 4.5 copper hydrate 1 1.01% 300 8.00 2100 4.5 copper hydrate 1 1.01% 300 7.14 2100 4.5 copper hydrate 2 2.01% 300 20.00 2100 4.5 copper hydrate 1 3.5% 300 5.00 10000 4.1 copper hydrate 3 1.2% 300 2.50 60000 3.8 copper hydrate 3 1.01% 300 no copper sulfate 100

* Both the copper complex solution and the freeze-dried material contained 8.57% copper, as in Example 12.

Example 18

As described in Example 2, copper complex solutions were tested on wheat kernels at concentrations of 0.15, 0.30 and 0.60 g Cu / kg, and the solution was applied to the core by spraying with laboratory equipment. The treated seeds were then air dried before planting.

seeds were planted in the soil for evaluation of germination and post-emergence growth. The assays were compared with a known copper-containing bactericidal / fungicidal preparation (Kocide Seed Dressing) at 0.60 g Cu / kg. Germination and growth were the same for all treatments (see Table 6), and no phytotoxicity was observed in the emerged seedlings.

Table 6

Treatment g / kg mag Germination% Kocide dressing 0.60 47 Example 2 0.15 48 Example 2 0.30 48 Example 2 0.60 48 untreated 0 45

Example 19

The copper complex solution prepared as described in Example 2 was applied to oranges at 100, 500 and 1000 ppm by immersing the fruits in the appropriate concentration and allowing the solution to dry on the surface. Before the fruits were dipped, they were inoculated with Altemaria citri, Phytophtora citrophthora, Penicillium digatatum and Colletotrichum gloesporioides. The fruits were stored at 5 ° C and 80% relative humidity for 14 days, and the number of diseased fruits was determined. At the end of the period, 100% of untreated fruits and 35, 10, and 8% of treated fruits were treated with 100, 500, and 1000 ppm copper complexes, respectively. No discoloration was observed on the fruit.

Example 20

Copper complex solutions prepared according to Example 2 were applied to geranium plants at 1000 ppm Cu at five times weekly intervals. At the end of the study period, evaluation was performed and compared with known amounts of known copper-containing bactericides / fungicides. Compared to treatments with known substances, there was no detectable residue on the plants. The plants were then subjected to an upper irrigation, and the evaluation was repeated after drying. Plants treated with the known fungicide had very visible residues on the treated plants, whereas there was no trace on the treatment with the copper complex according to the invention. In neither case was phytotoxicity 55 detectable.

Example 21

The copper complex prepared as described in Example 2 was applied to a cotton canvas cloth. Seed samples were treated with 1000 ppm tissue

It was immersed in copper complex solution and copper sulphate solution. For comparison, untreated tissue was used. The tissue samples were then embedded in non-sterile soil for two months. At the end of the study period, the untreated tissue was partially degraded, whereas the copper complex and copper sulfate treated tissue remained essentially intact.

Example 22

A copper complex solution was prepared as described in Example 3, except that the polyacrylic acid was neutralized to pH 3-6 using three different basic substances. The basic substances used are sodium hydroxide, potassium hydroxide and ammonium hydroxide. The samples contained 1% by weight of solid Goodrite K-752 polymer. The copper content of the various samples is determined and the results obtained are shown in Figure 5, where the copper concentration is plotted against the pH of the neutralized polyacrylic acid.

It is to be understood that the foregoing description relates to certain preferred embodiments of the present invention, and modifications that do not depart from the spirit of the invention are also within the scope of the invention.

Claims (15)

PATENT CLAIMS CLAIMS 1. A method of treating bacterial / fungal diseases in plants, comprising treating the plants with 0.1 to 6 kg of copper equivalent per ha of bacterial / fungal infections, comprising: a copper compound and a partially neutralized, water-soluble, 1000 to 300,000 an aqueous solution containing a molecular weight polycarboxylic acid complex, optionally together with a conventional excipient having a pH of from 3 to 9, a copper content of from 0.1 to 5% by weight, and a polycarboxylic acid content of from 0.2 to 80% by weight; solution is ammonia free and non phytotoxic to the plant. The process according to claim 1, wherein the polycarboxylic acid is selected from the group consisting of polyacrylic acid, polymethacrylic acid, copolymers of acrylic acid and acrylamide, copolymers of acrylic acid and methacrylamide, copolymers of acrylic acid and acrylic esters, acrylic acid and methacrylic acid, copolymers of esters, copolymers of acrylic acid and maleic anhydride, copolymers of carboxymethylcellulose, maleic acid and butadiene, polymers of maleic and maleic anhydride, copolymers of maleic acid and acrylic acid, copolymers of methyl vinyl ether and maleic anhydride. The process according to claim 1, wherein the polycarboxylic acid has a molecular weight of 2000 to 50000. The process according to claim 1, wherein the pH is adjusted to a value of 3.5-5. The process according to claim 1, wherein the copper-containing compound is selected from the group consisting of Cu (OH) ₂ , CuSO ₄ , Cu (C 10 ₄ ) ₂ , Cu ₂ O, Cu (NO ₃ ) ₂ , CuCl ₂ , tribasic copper sulfate, copper oxychloride, or basic copper carbonate. 6. The process of claim 5 wherein the copper-containing compound is selected from the group consisting of Cu (OH) ₂ , Cu ₂ O, tribasic copper carbonate, and copper oxychloride. The process of claim 1, wherein the copper compound is present in an amount of from 0.1 to 3.2% by weight of metal equivalent. The process according to claim 1, wherein the polycarboxylic acid is used in an amount of 0.75 to 20% by weight. 9. The method of claim 1, wherein the composition is for use against copper resistant bacterial plant pests. 10. A method for killing bacterial / fungal pests in crops, comprising applying to the crop, after harvesting, a bactericidal / fungicidal composition in an amount of 0.01 to 6.0 g of copper copper equivalent / kg comprising: a copper compound and a partially neutralized copper compound. water-soluble aqueous solution of a polycarboxylic acid complex having a molecular weight of 1000-300000, optionally together with the usual excipient having an aqueous solution having a pH of 3-9, a copper content of 0.1-5% by weight, and a polycarboxylic acid content of 0, 2 to 80% by weight, the solution is ammonia free and is not phytotoxic to the crop. 11. A method for killing bacterial / fungal pests in seeds, comprising treating the seeds with a bactericidal / fungicidal composition in an amount of 0.01 to 6.0 g of copper copper equivalent / kg before planting, comprising: a copper compound and a partially neutralized, water soluble An aqueous solution containing a polycarboxylic acid complex having a molecular weight of 1000-300000, optionally together with the usual excipient having an aqueous solution having a pH of 3-9, a copper content of 0.1-5% by weight, and a polycarboxylic acid content of 0.2- 80% by weight, the solution is ammonia free and non-phytotoxic to the seed. 12. A method for killing bacterial / fungal pests on ornamental plants, wherein the ornamental plants are treated with a bactericidal / fungicidal composition on their foliage in an amount of 0.01-6 kg of copper copper equivalent / ha comprising: a copper compound and a partially neutralized, water soluble 1000 An aqueous solution comprising a polycarboxylic acid complex having a molecular weight of about 300,000, optionally together with the usual excipient having an aqueous solution having a pH of from 3 to 9, a copper content of from 0.1 to 5% by weight and a polycarboxylic acid content from 0.2 to 80% by weight, the solution is ammonia free and non-phytotoxic to the plant. 13. A method for killing bacterial / fungal pests on a substrate comprising treating the substrate with a bactericidal / fungicidal composition in an amount of 1 to 1000 mg of copper equivalent / cm ² , comprising a copper compound and a partially neutralized water 12. A soluble aqueous solution of a polycarboxylic acid complex having a molecular weight of 1000-300000, optionally together with the usual excipient having an aqueous solution having a pH of from 3 to 9, having a copper content of 0.1 to 5% by weight of copper polycarboxylic acid. from 0.2 to 80% by weight, and the solution is ammonia free. 14. A non-phytotoxic bactericidal / fungicidal composition, comprising: - an aqueous solution of a copper compound and a partially neutralized, water-soluble, polycarboxylic acid complex having a molecular weight of 1000-300000 and having an aqueous solution having a pH of from 3 to 9, and the copper compound is Cu (OH) ₂ , CuSO ₄ , Cu ( C1O _{4) 2,} Cu ₂ O, Cu (NO _{3) 2,} CuC1 _2, tribasic copper sulfate, copper oxychloride or basic copper carbonate, copper compound expressed as a quantity of 0.1-5% fémrézekvivalensben,% amount of 0.2 to 80 parts by weight polycarboxylic acid, and 5 solutions are ammonia free and non phytotoxic to the plant, and - 0.1 to 10% by weight of a thickening agent that provides good adhesion to the copper complex to prevent rain from the plant surface or 10 reduced removal. 15. The bactericidal / fungicidal composition according to claim 14, wherein the thickening compound is selected from the group consisting of polyvinylpyrrolidone, polyethyleneoxy-leached derivative, polyvinyl alcohol and poly (acrylic). -amide).